Phosphorus containing esters of 2-hydroxyquinoxaline

ABSTRACT

PHOSPHORIC, THIONOPHOSPORIC, PHOSPHONIC, AND THIONOPHOSPHONIC ACID ESTERS OF 2-HYDROXYGUINOXALINE OF THE FORMULA   2-(R-O-P(=X)(-R&#39;&#39;)-O-)QUINOXALINE   IN WHICH R IS ALKYL, R&#39;&#39; IS ALKYL, ALKOXY OR PHENYL (SAID ALKYL AND ALKOXY HAVINGF 1 TO 4 CARBON ATOMS), AND X IS OXYGEN OR SULFUR, WHICH POSSESS PESTICIDAL, ESPECIALLY INSECTICIDAL AND ACARICIDAL, PROPERTIES AND WHICH MAY BE PRODUCED BY REACTING 2-HYDROXYQUINOXALINE WITH THE CORRESPONDING PHOSPHORUS-CONTAINING ESTER HALIDE.

United States Patent Int. Cl. covd 51/78 US. Cl. 260-450 R ClaimsABSTRACT OF THE DISCLOSURE Phosphoric, thionophosphoric, phosphonic, andthionophosphonic acid esters of 2-hydroxyquinoxaline of the formula inwhich R is alkyl, R is alkyl, alkoxy or phenyl (said alkyl and alkoxyhaving 1 to 4 carbon atoms), and X is oxygen or sulfur, which possesspesticidal, especially insecticidal and acaricidal, properties and whichmay be produced by reacting 2-hydroxyquinoxaline with the correspondingphosphorus-containing ester halide.

The present invention relates to particular new phosphorus-containingesters of 2-hydroxyquinoxaline, which have pesticidal, and especiallyinsecticidal and acaricidal, properties, to their pesticidalcompositions with dispersible carrier vehicles, and to methods for thepreparation and use thereof.

Open chain and cyclic quinoxaline-2,3-thiophosphoric acid esters arealready known from German Pat. No. 1,115,738. These products areobtained by reacting the corresponding 2,3-dimercaptoquinoxalines withalkylor aryl-phosphoric or -thionophosphoric acid monoester dihalides ordiester monohalides.

According to said German patent, the compounds in question arecharacterized by a good insecticidal and acaricidal activity; they havean especially strong action against resistant spider mites. However, theproduction of this group of active compounds is comparatively difficult,at least on an industrial scale.

It is an object of the present invention to provide particular newphosphorus-containing esters, such as phosphoric, thionophosphoric,phosphonic, and thionophosphonic acid esters of 2-hydroxyquinoxaline,which possess valuable pesticidal, and especially insecticidal andacaricidal, activity; to provide active compositions in the form ofmixtures of such compounds with solid and liquid dispersible carriervehicles; to provide a process for producing such compounds; and toprovide methods of using such compounds in a new Way, especially forcombating pests, such as insects and acarids, and the like.

Other and further objects of the present invention will become apparentfrom a study of the within specification and accompanying examples.

It has now been found, in accordance with the present invention, thatphosphoric, thionophosphoric, phosphonic, and thionophosphonic acidesters of Z-hydroxyquinoxaline having the formula 3,763,160 PatentedOct. 2, 1973 in which R is alkyl having 1 to 4 carbon atoms, R is amember selected from the group consisting of alkyl having 1 to .4 carbonatoms, lower alkoxy, and phenyl, and X is selected from the groupconsisting of oxygen and sulfur, possess strong pesticidal, andespecially insecticidal and acaricidal, properties.

It has been further found in accordance with the present invention thatthe particular new phosphorus-containing compounds of Formula I abovemay be produced by a process which comprises reacting2-hydroxyquinoxa1ine having the formula with phosphorus-containing esterhalides having the formula P-Hal R (IIb) in which R, R and X are thesame as defined above, and Hal is a halogen atom, including chlorine,bromine, fluorine, and iodine, and especially chlorine.

Advantageously, the particular new compounds of General Formula I havestrong arthropodicidal, i.e., insecticidal and acaricidal, properties,such as for instance an excellent activity against eating and suckinginsects, as well as an outstanding activity against spider mites andticks. The particular new compounds according to the present inventionare, in this respect, superior to the known products of analogousconstitution and having the same type of activity; therefore theyconstitute a genuine enrichment of the art.

The process for producing the particular new compounds of the presentinvention takes place according to the following equation:

X OR

In such equation, R, R, X and Hal have the same meanings as definedabove.

The process according to the present invention is preferably carried outwith the concurrent use of suitable solvents or diluents. Practicallyall inert organic solvents or mixtures thereof can be used for thispurpose, such as optionally halogenated hydrocarbons, for example,benzine, benzene, toluene, chlorobenzene and xylene; ethers, forexample, diethyl ether, dibutyl ether and dioxan; and ketones, forexample, acetone, methyl ethyl ketone, methyl isopropyl ketone and mehylisobutyl ketone. However, low boiling aliphatic alcohols, for example,methanol or ethanol, and, in particular, nitrile, for example,acetonitrile and propionitrile, as well as dimethyl formamide, haveproved to be especially suitable for this purpose.

Further, the reaction according to the present invention is preferablycarried out in the presence of acid acceptors. Practically all customaryacid-binding agents can be used for this purpose. Alkali metalalcoholates and carbonates, such as potassium and sodium methylate andethylate, and sodium and potassium carbonate, as well as tertiaryaliphatic, N-aliphatic-N-aromatic and heterocyclic amines, for example,triethylamine, dimethyl aniline and pyridine, have proved especiallyuseful.

The reaction temperature may be varied within a fairly wide range. Ingeneral, the reaction is carried out sub- 3 stantially between about 20and 120 C. (or the boiling point of the reaction mixture), preferably at40 to 80 C.

The starting materials and the auxiliaries (acid-binding agents) aregenerally used in stoichiometric quantities. After the startingcomponents have been mixed together, it is advantageous to continueheating the reaction mixture for some time (about 1 to 3 hours),possibly with stirring, in order to complete the reaction. By thismethod, the products of the present process are obtained in excellentyields and with a high degree of purity.

Some of the esters according to the present invention are colorlesscrystals with a sharp melting point; if necessary, these can easily befurther purified by recrystallization from conventional solvents. Inmost cases, however, the compounds are colorless to yellow colored,viscous, water-insoluble oils which cannot be distilled withoutdecomposition but which can be freed from the last volatile componentsand purified in this way by a so-called partial distillation, i.e. byprolonged heating at moderately elevated temperatures under reducedpressure. Determination of the refractive index may serve for a morespecific characterization.

As has already been mentioned above, the products of the present processare characterized by an outstanding insecticidal and acaricidalactivity. At the same time, they have only a low toxicity towardswarm-blooded animals and a low phytotoxicity. The eifect appears rapidlyand is long-lasting. The compounds according to the present inventioncan, therefore, be used with good results in plant protection forcombating noxious sucking and eating insects and Diptera and in thisfield, as well as in veterinary medicine, against mites (Acarina). Theexcellent activity of the particular new compounds against strains ofspider mites which are resistant to phosphoric acid esters is to beespecially emphasized.

The sucking insects contemplated herein essentially include aphids, suchas the peach aphid (Myzus persicae) and the black bean aphid (Dora'lz'sfabae); coccids, such as Aspidiotus hederae, Lecanz'um hesperidum andPseudococcus maritimus; Thysanoptera, such as Hercinothrips femoralis;and bugs, such as the beet bug (Piesma quadrata) and the bed bug (Cimexlectularius); and the like.

The eating inspects contemplated herein essentially include butterflylarvae, such as Plutella maculipennis and Lymantria dispar; beetles,such as grain weevils (Sitaphilus granarius) and the Colorado beetle(Leptintarsa decemlineata); and also species living in the soil, such aswire worms (Agriotes sp.) and cockchafer larvae (Mololontha melolontha);cockroaches, such as the German cockroach (Blatella germanz'cw);Orthoptera, such as the cricket (Gryllus domesticus); termites, such asRecticulitermes; and Hyrnenoptera, such as ants; and the like.

The Diptera contemplated herein mainly comprise the flies, such as thefruit fly (Drosophila melanogaster), the Mediterranean fruit fly(Ceratitis capitata) and the house fly (Musca domestica); gnats, such asthe mosquito (Aedes aegypti); bluebottlc flies, such as the gold fly(Lucilia sericata); and blowflies (Chrysomya' chloropyga); and the like.

Among the mites contemplated herein, the spider mites (Tetranychidae)are of special importance, such as the common spider mite (T etranychusurticae) and the fruit tree spider mite (Paratetranychus pilosws); gallmites, such as the red currant gall mite (Eriophyes ribis) andtarsonemides, such as Twrsonemus pallidus; and also ticks, such asBoo'philus microplus and scrab mites; and the like.

Advantageously, the active compounds according to the present inventionare equally suitable as insecticides and acaricides in plant protectionand also for combating hygiene pests, for example, in homes, stables andstore rooms.

Thus, the new compounds of the instant invention can be used aspesticides either alone or in admixture with solid or liquid carriers ordiluent.

The active compounds according to the instant invention can be utilized,if desired, in the form of the usual formulations or compositions withdispersible carrier vehicles, such as solutions, emulsions, suspensions,emulsifiable concentrates, spray powders, pastes, soluble powders,dusting agents, granulates, etc. These are prepared in known manner, forinstance by extending the active agents with dispersible liquid diluentcarriers and/or dispersible solid carriers optionally with the use ofcarrier vehicle assistants, e.g., surface-active agents, includingemulsifying agents and/or dispersing agents, whereby, for example, inthe case where water is used as diluent, organic solvents may be addedas auxiliary solvents (of. Agricultural Chemicals, March 1960, pages35-38). The following may be chiefly considered for use as carriervehicles for this purpose: dispersible liquid diluent carriers, such asaromatic hydrocarbons (for instance, benzene, toluene, Xylene, etc),halogenated, especially chlorinated, aromatic hydrocarbons (forinstance, chlorobenzenes), paraffins (for instance, petroleumfractions), chlorinated aliphatic hydrocarbons (for instance, methylenechloride, etc.), alcohols (for instance, ethanolamine, etc.), amides(for instance, dimethyl formamide, etc.), sulfoxides (for instance,dimethyl sulfoxide, etc.), ketones (for instance, acetone, etc.), andWater; as well as dispersible finely divided solid carriers, such asground natural minerals (for instance, kaolins, alumina, silica, chalk,i.e., calcium carbonate, talc, kieselguhr, etc.) and ground syntheticminerals (for instance, highly dispersed silicic acid, silicates, e.g.,alkali silicates, etc); whereas the following may be chiefly consideredfor use as carrier vehicle assistants, e.g., surface-active agents, forthis purpose: emulsifying agents, such as non-ionic and anionicemulsifying agents (for instance, polyethylene oxide esters of fattyacids, polyethylene oxide ethers of fatty alcohols, alkyl sulfonates,aryl sulfonates, etc., and especially alkyl arylpolyglycol ethers,magnesium stearate, sodium oleate, etc.); and dispersing agents, such aslignin, sulfite waste liquors, methyl cellulose, etc.

As will be appreciated by the artisan, the active compounds according tothe instant invention may be present in such formulations orcompositions in the form of mixtures with one another and with otherknown active substances, if desired.

The substances according to the invention may be em ployed by themselvesas the artisan will appreciate, in the form of their compositions withsolid or liquid dispersible carrier vehicles or other known compatibleactive agents, or in the form of particular dosage preparations forspecific application made therefrom, such as solutions, emulsions,suspensions, powders, pastes, and granulates which are thus ready foruse.

As concerns commercially marketed preparations, these generallycontemplate carrier composition mixtures in which the active compound ispresent in an amount substantially between about 01-95% by weight, andpreferably 05-90% by weight, of the mixture, whereas carrier compositionmixtures suitable for direct application or field application generallycontemplate those in which the active compound is present in an amountsubstantially between about 0.000001 and 20%, preferably 0.00001 and 5%,by Weight of the mixture. Thus, the present invention contemplatesover-all compositions which comprise mixtures of a dispersible carriervehicle, such as (1) a dispersible carrier solid, or (2) a dispersiblecarrier liquid preferably including a carrier vehicle assistant, e.g.,surface-active agent, such as an emulsifying agent and/or a dispersingagent, and an amount of the active compound which is effective for thepurpose in question and which is generally between about 0.000001 and byweight of the mixture.

Furthermore, the present invention contemplates methods of combatingpests, especially insects and acarids, which comprise applying to atleast one of (a) such pests and (b) their habitat, a pesticidally,especially insecticidally and/or acaricidally, effective amount of theparticular active compound of the invention alone or together with acarrier vehicle, as noted above. The instant formulations orcompositions are applied in the usual manner, for example, by spraying,atomizing, scattering, dusting, watering, sprinkling, vaporizing, andfumigating, and the like. It will be realized in accordance with thepresent invention that the instant compounds may be used elfectively notonly in plant protection, but also in hygiene control, especiallyagainst insects and acarids.

The outstanding pesticidal, and especially insecticidal and acaricidal,activity of the particular new compounds of the present invention can beseen from the following examples:

EXAMPLE 1 Myzus test (contact action) Solvent: 3 parts by weight acetoneEmulsifier: 1 part by weight alkylaryl polyglycol ether To produce asuitable preparation of the particular active compound, 1 part by weightof such active compound is mixed with the stated amount of solventcontaining the stated amount of emulsifier, and the concentrate isdiluted with water to the desired final concentration.

Cabbage plants (Brassica oleracea) which have been heavily infested withpeach aphids -(Myzus persicae) are sprayed with the stated preparationof the given active compound until dripping wet.

After the specified period of time, the degree of destruction isdetermined percentagewise: 100% indicated that all the aphids arekilled, whereas indicates that none are killed.

The active compounds, their concentration, the evaluation time and theresults obtained can be seen from the following Table 1:

TABLE 1.PLANT DAMAGING INSECTS Percent Conceu- Degree tration ofdeofactive struction comafter 24 Active compound pound hours (III) O0.01 100 N I] 0.001 20 To-nooma,

)o-moonzrm (V) N 1S OCzHs 0 13g S OCH 0.1 100 (VI) N Ii/ 2 5 0.01 08 0P\0.001 60 II S OCH-iso 0.1 100 (V N II/ a 7 0.01 100 O-P\ 0.001 90 OCH:

TABLE 1C0ntinued Percent Coucen- Degree tration of deof active structionI comafter 24 Active compound pound hours (VIII) N i/O C2115 0.1 0. 01100 o-P 0. 001 100 (IX) 0 0.1 100 I S 0. 01 40 ll I]Q'OH2 C2 5)a N(Compound known from U.S. patent specification No. 2,758,135.)

EXAMPLE 2 Tetranychus test Solvent: 3 parts by weight acetoneEmulsifier: 1 part by weight alkyl aryl polyglycol ether.

To produce a suitable preparation of the particular active compound 1part by Weight of such active compound is mixed with the stated amountof solvent containing the stated amount of emulsifier, and theconcentrate is diluted with water to the desired final concentration.

Bean plants (Phaseolus vulgaris), which have a height of approximately10-30 cm., are sprayed with the stated preparation of the given activecompound until dripping wet. The bean plants are heavily infested withcommon spider mites (Tetranychus urticae) in all stages of development.

After the specified period of time, the effectiveness of the particularpreparation of active compound is determined by counting the dead mites.The degree of destruction is expressed percentagewise: 100% indicatesthat all the spider mites are killed, whereas 0% indicates that none arekilled.

The active compounds, their concentrations, the evaluation time and theresults obtained can be seen from the following Table 2:

TABLE 2C0ntinued TABLE 3-Continued Percent Percent Concen- DegreeConoen- Degree tration of detration of de of active stfrgctioirsi 5 ofactive strritictiori COIH- a I COIII- a er Active compound pound hoursActive compound pound days (XII) N 0 0C H iso 0.1 100 (VI') N s 0021150.001 100 g 0.01 90 0.0001 75 OCH; 10 OBHB \N/ \N/ W111 N o c211, 0 1 3(VIII"). N fi 002m .8g} 1 g o-1 OP 0.00001 70 CH; CH; \N/ \N/ (IX) 0 0.1 100 (IX) 0 0. 001 100 s 0. 01 0 ll 0.0001 0 1 ll NCHzS-P(OC2H5)2N-CH2S'P(OC2H5)9 I 1 s: V

(Compound known from U.S. patent D known from Patent specification No.2,758,115.) specification No. 2,758,115.)

EXAMPLE 3 EXAMPLE 4 Plutella est Boophilus test Solvent: 3 parts byweight acetone Solvent: 3 parts by welght acetone Emulsifier: 1 part byWeight alkylaryl polyglycol ether. Emulslfier' 1 Part by Weightalkylaryl Polyglycol ether To produce a suitable preparation of theparticular acg 22233 21 i s: g gi i g? tyf ihe zcfiie r tive compound, 1part by weight of such active compound pound is mixed vvith the stzitedimount of the solvent is mixed with the stated amount of solventcontaining the stated amount of emulsifier, and the concentrate is t g fl -g i and the congendiluted with water to the desired finalconcentration. m e l u e Wa er to esl-red final concentration Cabbageleaves (Brassica oleracea) are sprayed with 40 Ten female tlcks Rmwroplus.) are Placfid on the preparation of the given active compounduntil dew a small g which Is sui-uwquenfly Immersed m the re moist, andare then infested with caterpillars of the p a 6 active compound Afterone diamondback moth (Plutella maculipennis). e 3 fi mm the After thespecified period of time, the degree of deplaced m i contammg filterpaper The tlcks 1' struction 1s determined percentagewrse: 100%indicates g gf zg g g gg zggg i glf g g g q fi that all of thecaterpillars are killed, Whereas 0% indid t d t p d p f 9 0 cates thatnone are killed. flestrulci iofntif e irmme percentagewlse. 10 0%1nd1cates The active compounds, their concentrations, the evalui z S areklned whereas 0% Indicates that ation time and the results obtained canbe seen from the Th f ll i Table 3: e actlve compounds, theirconcentrations and the results obtained can be seen from the followingTable 4:

TABLE 3 PLANT DAMAGING INSECTS TABLE 4.PLANT DAMAGING INSECTS.

Percent Percent Concen- De ca 03253: lgfeggze tuition of 1 1eofactivestruetion M8321: ggigg tter 4 Active com ound d h ur Active compoundpgii d a days p polm o s (III').---. 0.5 100 (111)- 0. 001 100 /N [I 00,5 25 N il w zmh 0. 0001 so 0 0 (IV 0.0 2 (1V") N S 0. 0001 100 N H 0.030 28 0-i oo2115 (V) 8 00,11. 0. 0005 100 (V").-.-..- s 00 H 0.0001 100N N 0 2 5 0.00001 20 o-i 000025 65 \CZHi CzHs \N/ TABLE 4C0ntlnued TABLE4a-Continued Percent Percent Concen- Degree Concen- Degree tration ofdetration of deof active struetion of active struction comafter 72 5comafter 72 Active compound pound hour Active compound pound hours (VI)S OCIHE 0- 001 100 (VII").... N s 003111-150 0.1 100 N 0. 00025 55 0 P0.01 95 08115 OCH: N

(X)....' s OCH; 1.0 100 (V"').... s 002B; 0.1 100 ll 0.01 95 OCH; CH: N

(VII) N fi/OCH: 0% 128 (V'"')...- N fi/OCzHr 0 1% 0-P OP\ 0.001 100O-is0-CaH1 02H \N/ \N/ The following examples are given for the purposeof illustrating the production process in accordance with the invention:EXAMPLE 4a EXAMPLE 5 Drosophila test Solvent: 3 parts by weight acetoneN a Emulsifier: 1 part by weight alkylaryl polyglycol ether.

To produce a suitable preparation of active compound, 1 part by weightof the active compound is mixed with um the stated amount of solventcontaining the stated amount of emulsifier and the concentrate isdiluted with water to 5 9 grams (0.4 mol) of 2-hydroxyquinoxaline areheated the desired concentration. under reflux, together with anequimolar amount of dried,

1 cc. of the preparation of the active compound is finely sievedpotassium carbonate, in 350 ml. of acetoniapplied with a pipette to afilter paper disc of 7 cm. diamtrile for 15 minutes, while stirring, and60 g. of 0,0-dieter. The wet disc is placed in a glass vessel containing50 ethyl-phosphoric acid ester chloride are subsequently addfruit flies(Drosophila melanogaster) and covered with a ed dropwise to the reactionmixture at 50 to 55 C. glass plate. The reaction mixture is stirred fora further 2 hours After the specified periods of time, the destructionis at 75 C., allowed to cool, mixed with 500 ml. of benzene determinedas a percentage: 100% means that all the and the soluble components arewashed out by shaking flies are killed; 0% means that none are killed.several times with water. The organic phase which results The activecompounds, their concentrations, the evaluais dried over sodium sulfateand the solvent evaporated tion times and the degree of destruction canbe seen from under reduced .pressure, finally using a so-called .partialthe following table: distillation at 70 C. and 0.1 mm. Hg.

In this way, 94 g. (83.5% of theory) of 0,0-diethylphosphoric acid-O-[quinoxalyl-(2)] ester are obtained in the form of a yellowish oil whichcannot be distilled with- TABLE DAMAGING INSECTS out decomposition andwhich has the refractive index Percent "D25 1.5383. Comm DegreeAnalysis.Calcd. for C H N O P (molecular weight tration of de- 282.2)(percent): N, 9.92; P, 10.97. Found (percent): N, ofactiye stfilctiolr 02. 11 12 61 Active compound pg ri d 8 hours EXAMPLE 6 (IXI//) S 0.1 0 Ns OCIH u 4 (C2H5Q)zPS-CH2-N I 01H: N

N/ \N /n (Compound known from US. patent 44 grams (0.3 mol) ofZ-hydroxyquinoxaline are stirred speclficatwn 217581115 with 750 ml. ofdimethyl formamide and an equivalent (mun) O 0 1 100 amount of amethanolic sodium methylate solution is /N m 1 added to this mixture,which is then concentrated under O-P (0 CzHs): reduced pressure to avolume of 200 ml.

The resultant solution is mixed dropwise at 60 C. with 66 g. ofphenyl-thionophosphonic acid-O-ethyl ester chlo- 70 ride andsubsequently further stirred at to C. for s 0,1 100 two hours. Workingup of the reaction mixture as in Ex- N H 0.01 100 am le 5 ives (86% oftheor of hen l-thionop s g y p y O 0'001 phosphonicacrd-O-ethyl-O-[quinoxalyl-(Z)] ester in the form of white crystalswhich melt at 142 C., after recrys- 75 tallization from benzene/ligroin.

11 Analysis.-Calcd. for C H N O PS (molecular weight 330.4) (percent):P, 9.39; S, 9.71. Found (percent): P, 9.75; S, 9.89.

EXAMPLE 7 S OCzHs A 0.1 Q ocaHu N (IV') 10 51 grams (0.35 mol) of2-hydroxyquinoxaline are stirred into 400 ml. of acetonitrile andbriefly boiled with 36 g. of triethylamine. 66 grams of0,0-diethyl-thionophosphoric acid ester chloride are added dropwise tothis mixture, which is subsequently stirred for a further two hours,while boiling under reflux. Working up of the reaction mixture iscarried out in the manner described in Example 5. 85 grams (81.5% oftheory) of 0,0-diethyl-thionophosphoric acid-O-[quinoxalyl-(2)] esterare obtained in the form of a dark-yellow oil which has the refractiveindex 11 1.5624, and which decomposes when distilled. M.P. 3536 C. (fromligroin).

Analysis.-Calcd. for C H N O PS (molecular weight 298.3 (percent): P,10.38; S, 10.75. Found (percent): P, 10.56; S, 10.75.

EXAMPLE 8 The following compounds of the general formula:

are obtained in a manner analogous to that described in 12 The compound,methyl-thionophosphonic acid-O-ethyl- O-[quinoxalyl-(2)] ester, has theformula The compound, ethyl-thionophosphonic acid O ethyl-O-[quinoxalyl-(2)] ester, has formula EXAMPLE 9 In the same manner,using corresponding molar amounts of 2-hydroxyquinoxaline and each ofthe following starting materials, respectively:

(a) 0,0-di-n-propyl-phosphoric acid ester chloride;

(b) 0,0-di-tert.-butyl-phosphoric acid ester chloride;

(c) 0,0-diisopropyl-thionophosphoric acid ester chloride;

(d) 0,0-di-sec.-butyl-thionophosphoric acid ester chloride;

(e) methyl-phosphonic acid-O-tert.-butyl ester chloride;

(f) isobutyl-phosphonic acid-O-n-propyl ester chloride;

(g) n-propyl-thionophosphonic acid-O-n-butyl ester chloride;

(h) sec.-butyl-thionophosphonic acid-O-isopropyl ester chloride;

(i) phenyl-phosphonic acid-O-methyl ester chloride;

(j) phenyl-phosphonic acid-O-tert.-butyl ester chloride;

(k) phenyl-thionophosphonic acid-O-isopropyl ester chloride;

(1) phenyl-thionophosphonic acid-O-n-butyl ester (VII!!!) Examples 5 to7. chloride;

Analysis, percent Molec- Oalcd. Found Yield, Physical ular percentconstants R R Empirical formula weight P S P S of theory my OH (X)- C HNm PS 270. 2 11. 46 11. 87 11. 73 12. 71 1. 5573 C1zH Nz0 PS 298. 1 10.38 10. 70 9. 56 9. 99 82 1. 5603 OnHraNzOzPS 268. 2 11. 60 11. 90 13. 1013. 40 69 1. 5768 CmHusNaOzPS 282. 3 10. 90 11. 36 11. 7 11. 25 78 1.5802 The compound, 0,0-dimethyl-thionophosphoric acid-O-[quinoxalyl-(2)] ester, has the formula The compound, O-methyl Oisopropyl-thionophosphoric acid O [quinoxalyl-(2)] ester, has theformula (VI/H) the particular phosphoric, thionophosphoric, phosphonic,and thionophosphonic acid esters, respectively, are formed:

(h') sec.-butyl-thionophosphonic acid-O-iso-propyl- [quinoxalyl-(Z)ester;

(i) phenyl-phosphonic acid-O-methyl-O-[quinoxalyl-(2)] ester;

(j') phenyl-phosphonic acid-O-tert.-butyl-O-[quinoxalyl-(2)] ester;

(k') phenyl-thionophosphonic acid-O-iso-propyl- O-[quinoxalyl-(2)]ester;

(1') phenyl-thionophosphonic acid-O-n-butyl-O- [quinoxalyl-(2)] ester.

It will be appreciated, in accordance with the present invention, thatin the foregoing formulae:

R represents alkyl having 1 to 4 carbon atoms, such as methyl, ethyl,n-propyl, iso-propyl, n-butyl, isobutyl, secwbutyl, tert.-butyl, andparticularly alkyl having 1 to 3 carbon atoms, i.e., methyl, ethyl,n-propyl, and iso-propyl;

R' represents alkyl having 1 to 4 carbon atoms, such as methyl totert.-butyl, inclusive, i.e., the radicals specifically mentioned underR, and particularly alkyl having 1 to 3 carbon atoms, i.e., methyl,ethyl, npropyl, and iso-propyl; lower alkoxy, such as methoxy, ethoxy,n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec.-butoxy, tert.-butoxy,and the like, and particularly alkoxy having 1 to 3 carbon atoms,including methoxy, ethoxy, n-propoxy and iso-propoxy; or phenyl; and

X represents oxygen or sulfur, preferably sulfur.

In accordance with a preferred feature of the invention, R is C -Calkyl; R is C -C alkyl, C -C alkoxy, or phenyl; and X is oxygen orsulfur, preferably sulfur.

Thus, the preferred subgeneric aspects of the present inventioncontemplate:

O,O-di(C C alkyl) phosphoric acid O [quinoxalyl-(2)] ester having theformula O,O-di(C -C alkyl-thionophosphoric acid-O- [quinoxaly-( 2)]ester having the formula C -C alkyl-phosphonic acid-O-(C -Calkyl)-O-[quins O-(C -C4 alkyl) C -C alkyl-phosphonic acid-O-(C -Calkyl)-O-[quinoxalyl- (2)] ester having the formula C -Calkyl-thionophosphonic acid-O-(C -C alkyl)-O'- [quinoxalyl-(2)] esterhaving the formula Phenyl-phosphonic acid O (C -C alkyl) O[quinoxalyl-(2)] ester having the formula 14 Phenyl-thionophosphonicacid 0 (C 43 alkyl)-O- [quinoxalyl-(2)] ester having the formula All ofthe foregoing compounds contemplated by the present invention possessthe desired pesticidal, and especially insecticidal and acaricidal,activity, whereby the combating of pests, such as arthropods, may beattained effectively.

It will be appreciated that as contemplated herein, the terms artropod,arthropodicidal and arthropodicide may be defined as encompassingspecifically both insects and acarids within the comtemplation of theirmeaning, for convenience in determining the collective aspects ofutility herein. Thus, the insects and acarids may be considered hereincollectively as arthropods to be combated collectively in accordancewith the invention, and accordingly the insecticidal and/or acaricidalactivity may be termed arthropodicidal activity, and the concomitantcombative or effective amount used in accordance with the invention willbe an arthropodicidally effective amount which in essence means aninsecticidally or acaricidally effective amount of the active compoundfor the desired purpose.

It will be appreciated that the instant specification and examples areset forth by way of illustration and not limitation, and that variousmodifications and changes may be made without departing from the spiritand scope of the present invention.

What is claimed is:

1. A phosphorus-containing ester of Z-hydroxyquinoxaline having theformula in which R is alkyl having 1 to 4 carbon atoms, R is a memberselected from the group consisting of alkyl having 1 to 4 carbon atoms,lower alkoxy having 1 to 4 carbon atoms, and phenyl, and X is selectedfrom the group consisting of oxygen and sulfur.

2. An ester according to claim 1 wherein R is alkyl having 1 to 3 carbonatoms, R is a member selected from the group consisting of alkyl having1 to 3 carbon atoms, lower alkoxy having 1 to 3 carbon atoms, andphenyl, and X is sulfur.

3. An ester according to claim 1 wherein such compound is0,0-diethyl-phosphoric acid-O-[quinoxalyl-(2)] ester having the formula4. An ester according to claim 1 wherein such compound is 0,0-diethylthionophosphoric acid O [quinoxalyl-(2)] ester having the formula 5. Anester according to claim 1 wherein such compound isethyl-thionophosphonic acid-O-ethyl O [quinoxa1yl-(2)] ester having theformula 5 0-CgH5 6. An ester according to claim 1 wherein such compoundis phenyl-thionophosphonic acid-O-ethyl-O-[quinoxalyl-(2)]ester havingthe formula 8. An ester according to claim 1 wherein such compound isO-methyl-0-iso-propyl-thionophosphoric acid-O [quinoxa1y1-(2)] esterhaving the formula 16 9. An ester according to claim 1 wherein suchcompound is methyl-thionophosphonic acid-O-ethyl-O-[quinoxalyl-(2)]ester having the formula 10. A compound of the formula wherein R and Rare selected from the group consisting of alkoxy radicals of up to 4carbon atoms.

References Cited UNITED STATES PATENTS 25 3,150,149 9/1964 Uhlenbroek eta1. 260-310 3,172,888 3/1965 Miller et al. 260250 3,216,894 11/1965Lorenz et al. 260250 3,340,262 9/1967 Gagliardi et al. 260250 ALEXMAZEL, Primary Examiner R. V. RUSH, Assistant Examiner US. Cl. X.R.

I UNITED STATES PATENT OFFICE 89 CERTIFICATE OF CORRECTION Patent No. 3,763,l60 Dated October 2, 19 73 Inventor(5) Karl-Julius Schmidt et a1 Itis certified that error appears in the above-identified patent w andthat said Letters Patent are hereby corrected as shown below:

' Col, 3, line correct spell ing of '"scab".

CO1.6', line 20, change "2 ,7 58',l35"- -to" 2 ,758,, 115

Col. 7, line 31, correct spelling of" 'j'tes't".

-Col. 8, line 13 in the Table -change'."0-. 001," (se cond'occurrence)COL-l3, line 37 correct formula (I) as follows: change s "4' to o v u' nCold 13 delete lin'efib.

. Signed and sealed this 24th day of September 1974. I

(sEA L) Attestz, I

McCOY M. GIBSON JR. c. MARSHALL DANN Attesting Officer CommissionerofPaterlts

